JP4580066B2

JP4580066B2 - Fluororesin laminate and molded body comprising the same

Info

Publication number: JP4580066B2
Application number: JP2000209110A
Authority: JP
Inventors: 正道赤津; 収二寺崎; 久明寺島
Original assignee: Kureha Corp
Current assignee: Kureha Corp
Priority date: 2000-07-10
Filing date: 2000-07-10
Publication date: 2010-11-10
Anticipated expiration: 2020-07-10
Also published as: JP2002019051A

Description

【０００１】
【発明の属する技術分野】
本発明はフッ化ビニリデン系樹脂及びアクリル系樹脂の樹脂組成物からなる表層と特定な物性を有するアクリル系樹脂からなる２層構成を有するフッ素系樹脂積層体及びそれからなる成形体に関する。更に詳しくは、成形品表面の微少な皺、外力による割れ等が生じ難く、特に自動車等車輌や家具、建材の内外表装材料に好適なフッ素系樹脂積層体及びそれからなる成形体に関する。
【０００２】
【従来の技術】
フッ素系樹脂フィルムは、耐候性、耐汚染性及び耐薬品性などに優れているため、プラスチック、ガラス、スレート、ゴム、金属板、木板、その他の基材表面の保護、装飾などの目的で表面保護フィルムとして使用されている。しかしながら、フッ化ビニリデン系フィルム単独では、結晶化速度が大きく、延伸した場合に白化したり、結晶性に由来する不都合が生じる。これを回避する為、フッ化ビニリデン系樹脂と他の樹脂との複合樹脂にして結晶性を調整することが行われている。特許第２５３０８３０号公報には、アクリル樹脂又はメタアクリル樹脂を５〜４０ＰＨＲ添加混合した弗化ビニリデン樹脂を第１層とし、前記アクリル樹脂又はメタアクリル樹脂と同一又は異なるアクリル樹脂又はメタアクリル樹脂を第２層とする２層積層体、若しくはこれに第３層として軟質塩化ビニル樹脂を貼り合わせ、その後１００〜１６０℃の温度で延伸した積層体の延伸成形物の発明が開示されている。また、特開平２−３０５２８号公報には、フッ化ビニリデン系樹脂１００〜５０重量部とメタクリル酸エステル系樹脂０〜５０重量部とを主成分とする樹脂組成物からなる表面層フィルムとフッ化ビニリデン系樹脂５０〜０重量部とメタクリル酸エステル系樹脂５０〜１００重量部を主成分とする樹脂組成物からなる中間層フィルム及び接着剤層の順に積層されたフッ素樹脂系多層フィルムの発明が開示されている。
【０００３】
【発明が解決しようとする課題】
本発明の目的は、可塑剤を含む他の樹脂からなる成形体との粘着が起こり難く、耐薬品性を有する表面層を有し、外力で容易に割れ等を生じ難く、高温環境下で表面層に微少な皺が発生し難く、耐熱性を有するフッ素系樹脂積層体及びそれからなる成形体、特に自動車等車輌の内外装材料に好適なフッ素系樹脂積層体及びそれからなる成形体を提供することにある。
【０００４】
【課題を解決するための手段】
本発明者らは、上記の課題を達成するために検討した結果、特定割合のフッ化ビニリデン系樹脂及びアクリル系樹脂からなる表層と特定物性を有するアクリル系樹脂からなる層との積層体がかかる問題点を解決しうることを見い出し、本発明を完成するに至った。
【０００５】
すなわち本発明は、フッ化ビニリデン系樹脂３０〜７０重量部、アクリル系樹脂３０〜７０重量部（両者の合計は１００重量部とする）の樹脂組成物からなる表面層である第１層、ＡＳＴＭＤ６３８による破断伸度２０％以上、且つＡＳＴＭＤ５０２６による粘弾性測定から求められるｔａｎδのピーク値が１００〜１５０℃であるアクリル系樹脂からなる第２層がこの順序に配置された少なくとも２層構成を有するフッ素系樹脂積層体を提供する。前記発明において第２層の第１層と反対側の面に加飾層を有するフッ素系樹脂積層体を提供する。前記発明の加飾層の第１層と反対側の面に熱可塑性樹脂からなる層を有するフッ素系樹脂積層体を提供する。前記発明のいずれかに記載のフッ素系樹脂積層体からなり、加熱成形時に２０〜５００％の伸張変形を受けた成形体を提供する。前記発明において第１層の厚さが１〜３０μｍである成形体を提供する。自動車等車輌、家具、建材、電気製品の部品である前記成形体を提供する。
【０００６】
【発明の実施の形態】
以下、本発明について詳しく説明する。
本発明の第１層で使用するフッ化ビニリデン系樹脂（以下、「ＰＶＤＦ］と略称することもある。）とは、フッ化ビニリデン単独重合体の他、フッ化ビニリデンを構成単位として５０モル％以上含有する共重合体、或いはこれら重合体の混合物を使用することができる。フッ化ビニリデンと共重合されるモノマーとしては、４フッ化エチレン、６フッ化プロピレン、３フッ化エチレン、３フッ化塩化エチレン、フッ化ビニル等が挙げられる。また、これらの１種または２種以上を用いることができる。また、前記ＰＶＤＦの溶融粘度としては、０．８×１０⁴〜７．０×１０⁴ポイズのものが好ましく、より好ましくは０．９×１０⁴〜６．０×１０⁴ポイズの範囲である。尚、本発明における溶融粘度は（株）東洋精機製作所製キャピログラフを使用し、温度２４０℃、剪断速度５０ｓｅｃ^-1の条件で測定した値である。
【０００７】
本発明の第１層に用いられるアクリル系樹脂は、アクリル酸又はメタクリル酸（以下、「（メタ）アクリル酸」と略称する。）の低級アルキルエステルより選ばれる少なくとも１種を主成分とする重合体又は共重合体であり、これらの（メタ）アクリル酸エステルとしては例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸ブチル等である。また、上記（メタ）アクリル酸エステルを主体に、好ましくは２５モル％以下、更に好ましくは１０モル％以下のエチレン系不飽和化合物との共重合体であってもよい。
【０００８】
本発明の第１層は、フッ化ビニリデン系樹脂３０〜７０重量部と前記アクリル系樹脂７０〜３０重量部（両者の合計は１００重量部とする）の樹脂組成物からなっている。ＰＶＤＦが３０重量部に満たないと耐薬品性が不充分となる。また、７０重量部を越えると積層体が伸ばされたときに、白化が発生することがある。第１層の厚さは、１〜５０μｍ程度、更には１〜３０μｍ程度が好ましい。
【０００９】
第２層を構成するアクリル系樹脂は、前記アクリル系樹脂から選ばれるがＡＳＴＭＤ６３８による破断伸度が２０％以上、好ましくは２０〜２００％、且つＡＳＴＭＤ５０２６による粘弾性測定から求められるｔａｎδのピーク値が１００〜１５０℃を有する。アクリル系樹脂が上記破断伸度２０％以下の場合、外力によるへこみ等の変形を受けた場合は割れが発生する。またｔａｎδのピーク値が１００℃未満の場合、耐熱性の低下により高温環境下で表面層の微少な皺が発生することがあるので好ましくない。ピーク値が１５０℃を越えると、特にインモールド成形を行う場合、熱変形がしにくく、良好な成形品が得られない場合がある。アクリル系樹脂からなる第２層は、積層体外部から受ける衝撃を吸収し、割れ、へこみの発生を防止すると共に、積層体の全体的或いは部分的伸びに対して歪みを分散し均一な伸びを生じさせる機能を有する。尚、第２層の樹脂には本発明の効果を損なわない範囲で、紫外線吸収剤、抗酸化剤、安定剤、顔料、その他の添加剤を適宜添加してもよい。
第１層と第２層とを合わせた厚さは１０〜３００μｍ、更には２０〜２００μｍが好ましい。
【００１０】
本発明の好ましい態様として第２層の第１層と反対側の面に加飾層を設けることができる。加飾層としては、印刷加工層、塗装等を挙げることができる。印刷方法としてはプラスチックフィルムに印刷する一般的な方法が適用できる。更に、加飾層の第１層と反対側の面側にインモールド成形やプレス成形等により熱可塑性樹脂からなる層を形成した積層体であってもよい。
【００１１】
熱可塑性樹脂としては、一般的な熱可塑性樹脂であれば制限はないが、例えば塩化ビニル系樹脂、ポリスチレン系樹脂、ＡＢＳ樹脂、ポリエステル系樹脂、ポリカーボネート系樹脂、ポリアミド樹脂、ポリウレタン樹脂、ポリプロピレン樹脂等が用いられ、特にＡＢＳ樹脂、ポリウレタン樹脂、ポリプロピレン樹脂、ポリスチレン樹脂等が成形性や価格の点で好ましい。
なお、必要であれば前記加飾層と熱可塑性樹脂層の間に接着剤層を設けてもよい。
【００１２】
本発明の積層体は、少なくとも２層積層体からなるが、積層体の製造は、通常、単層フィルムをそれぞれ製膜後熱ラミネートや接着剤によるドライラミネートで２層積層体を製造するか、又は共押出フィルム製造方法のＴダイ方式又はサーキュラーダイ方式のいずれによっても可能である。第２層の片面に加飾層、例えば印刷加工を施す場合は、２層体をつくり、第２層の面に印刷を施した後、印刷面に他の熱可塑性樹脂を接着層を介し、又は介することなく積層する。
本発明の積層フィルムにおいて表面層の厚さは１μｍ〜３０μｍの範囲であることが好ましく、第２層は１０μｍ〜２５０μｍの範囲が好ましい。また、第２層の片面に更に積層する熱可塑性樹脂からなる層は１０μｍ〜７００μｍの範囲が好ましい。積層体全体の厚さは特に制限はないが、５０μｍ〜３ｍｍが好ましい。こうして、前記の配合割合で第１層のフッ化ビニリデン系樹脂とアクリル系樹脂を混練し、別に第２層用のアクリル系樹脂を混練し、例えば、共押出でダイ内積層し、本発明の積層体を得ることができる。得られた積層体フィルムは充分な耐薬品性（可塑剤などを含む他の樹脂からなる成形品と表面層とのの融着が起こり難いこと）、及び耐熱性（表面層に微少皺が発生し難いこと）を有するので、自動車内外装材料等に好適に用いられる。
【００１３】
【実施例】
以下、実施例により本発明を具体的に説明するが、本発明はこれらに限定されるものではない。尚、評価方法は以下のように行った。
破断伸度：ＡＳＴＭＤ６３８に従って測定した。
ｔａｎδのピーク値の温度：ＡＳＴＭＤ５０２６に従い、レオメトリックス社製、ＲＳＡ−IIを用いて行った。
耐熱性を示す試験：１００℃の乾燥空気中に５００時間放置後、表面の皺の状態を観察する。
耐薬品性を示す試験：可塑剤（ＤＯＰ）を７０重量部含有したＰＶＣシート（３００μｍ厚）を１１０℃で４時間、サンプル表面に静置する。その後、シートを剥がしてサンプル表面に接着するかどうかを判定する。
衝撃試験：重さ５００ｇで先端がφ５ｍｍの半球形状の落錘を高さ３０ｍｍから自由落下させ、表面に亀裂、割れが発生するかどうかを目視判定した。○：亀裂又は割れなし、×亀裂又は割れあり。
インモールド成形時の白化：延伸による白化を目視判定した。○：白化なし、×：白化あり。
【００１４】
（実施例１）
第１層は、フッ化ビニリデン樹脂（呉羽化学工業（株）製、ＫＦ＃８５０）６０重量部、アクリル系樹脂（住友化学工業（株）製、スミペックスＭＥ、ＭＩ＝７）４０重量部の樹脂組成物を４０ｍｍ押出機（Ｌ／Ｄ＝２２フルフライトタイプ）で押出機温度２３０℃、第２層は、アクリル系樹脂（住友化学工業（株）製、スミペックスＨＴ−５５Ｘ、ＭＩ＝２、破断伸度７０％、ｔａｎδのピーク値１３３℃）単体を９０ｍｍ押出機（Ｌ／Ｄ＝２６，フルフライトタイプ）で押出機温度２５０℃でそれぞれ溶融した。これらをそれぞれ加熱された導管により、マルチマニフォールドタイプの幅１０００ｍｍの２層ダイに連結し、ダイ内で２層を積層し押出した。押出された２層構成溶融体を８０℃に加熱された金属鏡面ロールで冷却しながら全厚み８０μｍ（第１層１０μｍ）のフィルム状に引き取った。そのフィルムのアクリル系樹脂層側にグラビア印刷により、木目調の印刷を施した。次に、印刷されたフィルムを射出用の成形金型にインサートし、１３０℃に加熱しながら真空で引き、予め所定の形状に予備成形（約１００％程度の伸張変形を受ける）した。予備成形後、１６０℃に溶融した茶色に着色されたＡＢＳ樹脂を金型内に射出成形した。ＡＢＳ樹脂の厚みは３ｍｍであった。得られた成形体の層構成、性状の測定結果、耐薬品性、耐熱性、衝撃試験及びインモールド成形時の白化の評価結果を表１に示した。
【００１５】
（比較例１）
特開平２−３０５２８号公報の実施例２に準じて積層体を成形した。すなわち、第１層（厚み１６μｍ）のフッ化ビニリデン樹脂としてソーレフ１０１０（ソルベイ社製）、アクリル系樹脂としてアクリペットＭＤ（三菱レイヨン（株）製）の配合割合を表１に記載の通りとし、第２層（厚み２７μｍ）のアクリル系樹脂として同じアクリペットＭＤ（破断伸度７％、ｔａｎδのピーク値１３８℃）を用いた他は実施例１と同様にして成形体を得た。評価結果を表１に示す。
【００１６】
（比較例２）
特許第２５３０８３０号の実施例に準じて積層体を成形した。すなわち、第１層（厚み１μｍ）はフッ化ビニリデン樹脂（重合度Ｐ＝１０００、溶融粘度ηinh＝１．０：ＤＭＦ，３０℃）とアクリル系樹脂（分子量３０，０００、ＭＩ＝１．２７（ＡＳＴＭＤ１２３８）の配合割合を表１に記載の通りとし、第２層（厚み１０μｍ）としてアクリル系樹脂（分子量２７，０００、ＭＩ＝１．１（ＡＳＴＭＤ１２３８）、破断伸度１１０％、ｔａｎδのピーク値１０５℃）を用いた他は実施例１と同様にして成形体を得た。評価結果を表１に示す。
【００１７】
（比較例３）
第１層をＰＶＤＦ（呉羽化学工業（株）製、ＫＦ＃８５０）のみとしたことを除き、実施例１と同様に行った。評価結果を表１に示す。
【００１８】
（比較例４）
第２層にアクリル系樹脂（ＭＩ＝８、破断伸度１３０％、ｔａｎδのピーク値９５℃）を用いたことを除き、実施例１と同様に行った。
【００１９】
【表１】

【００２０】
【発明の効果】
本発明によれば、雰囲気温度が上昇した際、可塑剤などを含む他の成形品とべた付き、極端な場合には溶着などが生じ難く、また、熱による表面の微少皺の発生し難い成形体を与えることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a fluororesin laminate having a surface layer composed of a resin composition of vinylidene fluoride resin and an acrylic resin and a two-layer structure composed of an acrylic resin having specific physical properties, and a molded body composed thereof. More specifically, the present invention relates to a fluororesin laminate and a molded body comprising the same, which are suitable for interior and exterior surface materials of automobiles such as automobiles, furniture, and building materials, in which minute wrinkles on the surface of molded products, cracks due to external forces, and the like are unlikely to occur.
[0002]
[Prior art]
Fluorine-based resin films have excellent weather resistance, stain resistance, chemical resistance, etc., so they are used for the purpose of protecting and decorating the surfaces of plastics, glass, slate, rubber, metal plates, wood boards, and other substrates. Used as a protective film. However, the vinylidene fluoride film alone has a high crystallization rate, and when stretched, it becomes white or inconvenience due to crystallinity occurs. In order to avoid this, crystallinity is adjusted by using a composite resin of a vinylidene fluoride resin and another resin. In Japanese Patent No. 2530830, a vinylidene fluoride resin in which 5 to 40 PHR of an acrylic resin or a methacrylic resin is added and mixed is used as a first layer, and an acrylic resin or a methacrylic resin that is the same as or different from the acrylic resin or the methacrylic resin is used. An invention of a two-layer laminate having two layers, or a stretched product of a laminate in which a soft vinyl chloride resin is bonded to the third laminate and then stretched at a temperature of 100 to 160 ° C. is disclosed. JP-A-2-30528 discloses a surface layer film composed of a resin composition comprising 100 to 50 parts by weight of a vinylidene fluoride resin and 0 to 50 parts by weight of a methacrylic ester resin as a main component, and fluoride. Disclosed is an invention of a fluororesin multilayer film in which an intermediate film composed of a resin composition mainly composed of 50 to 0 parts by weight of a vinylidene resin and 50 to 100 parts by weight of a methacrylate ester resin and an adhesive layer are laminated in this order. Has been.
[0003]
[Problems to be solved by the invention]
The object of the present invention is to prevent sticking to a molded body made of another resin containing a plasticizer, to have a surface layer having chemical resistance, to prevent cracking easily by external force, and to form a surface in a high temperature environment. To provide a heat-resistant fluorine-based resin laminate and a molded body comprising the same, and particularly suitable for interior and exterior materials of automobiles such as automobiles, and a molded body comprising the same. It is in.
[0004]
[Means for Solving the Problems]
As a result of studies conducted by the present inventors to achieve the above-mentioned problems, a laminate of a surface layer composed of a specific proportion of vinylidene fluoride resin and acrylic resin and a layer composed of an acrylic resin having specific physical properties is applied. It has been found that the problems can be solved, and the present invention has been completed.
[0005]
That is, the present invention provides a first layer, ASTM, which is a surface layer composed of a resin composition of 30 to 70 parts by weight of vinylidene fluoride resin and 30 to 70 parts by weight of acrylic resin (the total of both is 100 parts by weight). It has at least a two-layer structure in which a second layer made of an acrylic resin having a tan δ peak value of 100 to 150 ° C. obtained from a viscoelasticity measurement by ASTM D5026 is 20% or more according to D638 and arranged in this order. Provided is a fluororesin laminate having the same. In the said invention, the fluorine resin laminated body which has a decorating layer in the surface on the opposite side to the 1st layer of a 2nd layer is provided. Provided is a fluororesin laminate having a layer made of a thermoplastic resin on the surface opposite to the first layer of the decorative layer of the invention. Provided is a molded body comprising the fluororesin laminate according to any one of the inventions and subjected to 20 to 500% elongation deformation during heat molding. In the above invention, a molded body having a first layer thickness of 1 to 30 μm is provided. Provided is the molded body which is a part of a vehicle such as an automobile, furniture, building materials, and electrical products.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be described in detail below.
The vinylidene fluoride resin (hereinafter sometimes abbreviated as “PVDF”) used in the first layer of the present invention is 50 mol% based on vinylidene fluoride as a constituent unit in addition to a vinylidene fluoride homopolymer. Copolymers containing the above or a mixture of these polymers can be used as monomers copolymerized with vinylidene fluoride, such as tetrafluoroethylene, hexafluoropropylene, trifluoride ethylene, trifluoride. Examples thereof include ethylene chloride, vinyl fluoride, etc. One or more of these may be used, and the PVDF has a melt viscosity of 0.8 × 10 ^{4 to} 7.0 × 10 ^4. is preferably a poise, more preferably in the range of 0.9 × 10 ^⁴ ~6.0 × 10 ⁴ poise. Incidentally, the melt viscosity in the present invention, Ltd. Toyo Seiki Seisakusho capillograph Use temperature 240 ° C., a value measured under the conditions of a shear rate of 50 sec ^-1.
[0007]
The acrylic resin used in the first layer of the present invention is a heavy resin mainly composed of at least one selected from lower alkyl esters of acrylic acid or methacrylic acid (hereinafter abbreviated as “(meth) acrylic acid”). These (meth) acrylates are, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, etc. . Further, it may be a copolymer with the above (meth) acrylic acid ester as a main component, preferably 25 mol% or less, more preferably 10 mol% or less of an ethylenically unsaturated compound.
[0008]
The first layer of the present invention is made from the resin composition of the acrylic resins 70-30 parts by weight of a vinylidene fluoride resins 30-70 parts by weight (the total of both is 100 parts by weight). If PVDF is less than 30 parts by weight, chemical resistance is insufficient. If it exceeds 70 parts by weight, whitening may occur when the laminate is stretched. The thickness of the first layer is preferably about 1 to 50 μm, more preferably about 1 to 30 μm.
[0009]
The acrylic resin constituting the second layer is selected from the above acrylic resins, but the elongation at break according to ASTM D638 is 20% or more, preferably 20 to 200%, and the peak value of tan δ determined from viscoelasticity measurement according to ASTM D5026 Has a temperature of 100 to 150 ° C. When the acrylic resin has a breaking elongation of 20% or less, cracking occurs when it is deformed by dents or the like due to external force. Moreover, when the peak value of tan δ is less than 100 ° C., it is not preferable because a slight wrinkle of the surface layer may occur in a high temperature environment due to a decrease in heat resistance. When the peak value exceeds 150 ° C., particularly when performing in-mold molding, thermal deformation is difficult, and a good molded product may not be obtained. The second layer made of acrylic resin absorbs the impact received from the outside of the laminate, prevents cracks and dents from being generated, and distributes the strain to the entire or partial elongation of the laminate to achieve uniform elongation. Has the function to generate. In addition, you may add a ultraviolet absorber, an antioxidant, a stabilizer, a pigment, and other additives suitably to the resin of 2nd layer in the range which does not impair the effect of this invention.
The total thickness of the first layer and the second layer is preferably 10 to 300 μm, more preferably 20 to 200 μm.
[0010]
As a preferred embodiment of the present invention, a decorative layer can be provided on the surface of the second layer opposite to the first layer. Examples of the decorative layer include a printed layer and coating. As a printing method, a general method for printing on a plastic film can be applied. Furthermore, the laminated body which formed the layer which consists of a thermoplastic resin by the in-mold shaping | molding, press molding, etc. on the surface side on the opposite side to the 1st layer of a decoration layer may be sufficient.
[0011]
The thermoplastic resin is not limited as long as it is a general thermoplastic resin. For example, vinyl chloride resin, polystyrene resin, ABS resin, polyester resin, polycarbonate resin, polyamide resin, polyurethane resin, polypropylene resin, etc. In particular, ABS resin, polyurethane resin, polypropylene resin, polystyrene resin and the like are preferable in terms of moldability and price.
If necessary, an adhesive layer may be provided between the decorative layer and the thermoplastic resin layer.
[0012]
The laminate of the present invention is composed of at least a two-layer laminate, but the production of the laminate usually involves producing a two-layer laminate by thermal lamination or dry lamination with an adhesive after each single-layer film is formed, Alternatively, either the T-die method or the circular die method of the coextruded film manufacturing method is possible. In the case of performing a decorative layer, for example, a printing process on one side of the second layer, after creating a two-layer body and printing on the surface of the second layer, another thermoplastic resin is applied to the printed surface via an adhesive layer, Or it is laminated without intervening.
In the laminated film of the present invention, the thickness of the surface layer is preferably in the range of 1 μm to 30 μm, and the second layer is preferably in the range of 10 μm to 250 μm. Further, the layer made of a thermoplastic resin further laminated on one side of the second layer is preferably in the range of 10 μm to 700 μm. Although the thickness of the whole laminated body does not have a restriction | limiting in particular, 50 micrometers-3 mm are preferable. Thus, the first layer vinylidene fluoride resin and the acrylic resin are kneaded at the above blending ratio, and the second layer acrylic resin is kneaded separately, for example, laminated in the die by coextrusion. A laminate can be obtained. The obtained laminated film has sufficient chemical resistance (the molded product made of other resin containing a plasticizer and the surface layer are less likely to be fused) and heat resistance (the surface layer is slightly wrinkled). Therefore, it is suitably used for automobile interior and exterior materials.
[0013]
【Example】
EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. The evaluation method was performed as follows.
Elongation at break: measured according to ASTM D638.
Temperature of peak value of tan δ: In accordance with ASTM D5026, it was carried out using RSA-II manufactured by Rheometrics.
Test showing heat resistance: After standing in dry air at 100 ° C. for 500 hours, the state of wrinkles on the surface is observed.
Test showing chemical resistance: A PVC sheet (300 μm thickness) containing 70 parts by weight of a plasticizer (DOP) is allowed to stand on the sample surface at 110 ° C. for 4 hours. Thereafter, it is determined whether the sheet is peeled off and adhered to the sample surface.
Impact test: A hemispherical falling weight with a weight of 500 g and a tip of φ5 mm was freely dropped from a height of 30 mm, and whether or not cracks and cracks occurred on the surface was visually determined. ○: No crack or crack, × crack or crack present.
Whitening at the time of in-mold molding: The whitening due to stretching was visually determined. ○: No whitening, ×: Whitening
[0014]
Example 1
The first layer is a resin of 60 parts by weight of vinylidene fluoride resin (manufactured by Kureha Chemical Industry Co., Ltd., KF # 850), 40 parts by weight of acrylic resin (manufactured by Sumitomo Chemical Co., Ltd., Sumipex ME, MI = 7). The composition was extruded with a 40 mm extruder (L / D = 22 full flight type) at an extruder temperature of 230 ° C., and the second layer was an acrylic resin (Sumipex HT-55X, MI = 2, broken by Sumitomo Chemical Co., Ltd.) A single unit of 70% elongation and tan δ peak value of 133 ° C. was melted with a 90 mm extruder (L / D = 26, full flight type) at an extruder temperature of 250 ° C. These were each connected by a heated conduit to a multi-manifold type two-layer die having a width of 1000 mm, and the two layers were laminated and extruded in the die. The extruded two-layer structure melt was taken up into a film having a total thickness of 80 μm (first layer: 10 μm) while being cooled with a metal mirror roll heated to 80 ° C. The film was printed on the acrylic resin layer side of the film by gravure printing. Next, the printed film was inserted into a molding die for injection, drawn in a vacuum while being heated to 130 ° C., and preliminarily formed into a predetermined shape (subjected to about 100% expansion deformation). After the preliminary molding, a brown colored ABS resin melted at 160 ° C. was injection molded into a mold. The thickness of the ABS resin was 3 mm. Table 1 shows the layer structure, property measurement results, chemical resistance, heat resistance, impact test, and whitening evaluation results during in-mold molding of the obtained molded body.
[0015]
(Comparative Example 1)
A laminate was molded according to Example 2 of JP-A-2-30528. That is, the blending ratio of Solef 1010 (manufactured by Solvay) as the first layer (thickness 16 μm) vinylidene fluoride resin and Acrypet MD (manufactured by Mitsubishi Rayon Co., Ltd.) as the acrylic resin is as shown in Table 1, A molded product was obtained in the same manner as in Example 1 except that the same acrylpet MD (breaking elongation: 7%, peak value of tan δ: 138 ° C.) was used as the acrylic resin for the second layer (thickness: 27 μm). The evaluation results are shown in Table 1.
[0016]
(Comparative Example 2)
A laminate was formed according to the example of Japanese Patent No. 2530830. That is, the first layer (thickness 1 μm) is composed of vinylidene fluoride resin (polymerization degree P = 1000, melt viscosity ηinh = 1.0: DMF, 30 ° C.) and acrylic resin (molecular weight 30,000, MI = 1.27 ( The blending ratio of ASTM D1238) is as shown in Table 1. As the second layer (thickness 10 μm), acrylic resin (molecular weight 27,000, MI = 1.1 (ASTM D1238), elongation at break 110%, tan δ Except for using a peak value of 105 ° C., a molded body was obtained in the same manner as in Example 1. Table 1 shows the evaluation results.
[0017]
(Comparative Example 3)
The same operation as in Example 1 was performed except that only the first layer was PVDF (manufactured by Kureha Chemical Industry Co., Ltd., KF # 850). The evaluation results are shown in Table 1.
[0018]
(Comparative Example 4)
The same operation as in Example 1 was performed except that an acrylic resin (MI = 8, breaking elongation 130%, tan δ peak value 95 ° C.) was used for the second layer.
[0019]
[Table 1]

[0020]
【The invention's effect】
According to the present invention, when the ambient temperature rises, it is sticky to other molded products containing a plasticizer, and in extreme cases, welding is not likely to occur, and molding is also difficult to generate surface flaws due to heat. Can give the body.

Claims

Breaking elongation according to ASTM D638, first layer which is a surface layer made of a resin composition of 30 to 70 parts by weight of vinylidene fluoride resin and 30 to 70 parts by weight of acrylic resin (the total of both being 100 parts by weight) Fluorine-based resin laminate having at least two layers in which a second layer made of an acrylic resin having a peak value of tan δ of 100% to 150 ° C. obtained from viscoelasticity measurement by ASTM D5026 is 20% or more and arranged in this order body.

The fluororesin laminate according to claim 1, further comprising a decorative layer on a surface of the second layer opposite to the first layer.

The fluororesin laminate according to claim 2 , wherein the decorative layer has a layer made of a thermoplastic resin on a surface opposite to the first layer.

A molded body comprising the fluororesin laminate according to any one of claims 1 to 3 and having undergone 20 to 500% expansion deformation during heat molding.

The molded body according to claim 4, wherein the first layer has a thickness of 1 to 30 μm.

The molded article according to claim 5, which is a part of a vehicle such as an automobile, furniture, building material, or electrical product.